CN104525133B - A kind of for N2metal-organic framework material of O absorption and preparation method thereof - Google Patents
A kind of for N2metal-organic framework material of O absorption and preparation method thereof Download PDFInfo
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- CN104525133B CN104525133B CN201510011665.7A CN201510011665A CN104525133B CN 104525133 B CN104525133 B CN 104525133B CN 201510011665 A CN201510011665 A CN 201510011665A CN 104525133 B CN104525133 B CN 104525133B
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02C—CAPTURE, STORAGE, SEQUESTRATION OR DISPOSAL OF GREENHOUSE GASES [GHG]
- Y02C20/00—Capture or disposal of greenhouse gases
- Y02C20/10—Capture or disposal of greenhouse gases of nitrous oxide (N2O)
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/151—Reduction of greenhouse gas [GHG] emissions, e.g. CO2
Abstract
A kind of for N2The metal-organic framework material of O absorption, chemical formula is { [(CH3)2NH2]19[Ni24(bptc)9(H2O)12(μ2‑O)12(μ3‑OH)4(μ4‑OH)3]·5H2O·DMA}n, in formula: n is 1 to the most infinite natural number, and bptc is 3,3 ', 5,5 ' biphenyl tetracarboxylic carboxylic acid ions, and DMA is N, N dimethyl acetylamide, (CH3)2NH2For dimethylamine cation；Its preparation method is by 3,3 ', and 5,5 ' biphenyl tetracarboxylic carboxylic acids, four hydration nickel acetates, a hydronium(ion) lithium oxide and concentrated nitric acid add in N, N dimethyl acetylamide and distilled water prepared after heating.The invention have the advantage that product preparation process is simple, easily operated, the metal-organic framework material of preparation has preferable soda acid and heat stability, and to N2O has higher adsorbance, can be used for N2The storage of O.
Description
Technical field
The present invention relates to metal-organic framework material technical field, particularly a kind of for N2The metal of O absorption has machine frame
Frame material and preparation method thereof.
Background technology
Climate change is the significant challenge that the current whole world faces, and the greenhouse gas emission that human society productive life causes is
The main cause of global warming.Containment climate warming, home of helping planet Earth, is the common mission of the whole mankind.In air
CO2、CH4And N2O is most important greenhouse gases, and the contribution rate of greenhouse effect be account for nearly 80%.Wherein CO2To strengthening greenhouse
The contribution rate of effect is maximum, accounts for 60%, is most important greenhouse gases.Next to that CH4, the contribution rate of greenhouse effect is accounted for
15%.N at present2O accounts for 5% to the contribution rate of greenhouse effect, but its warming effect is CO2296～310 times, CH44-
21 times.N2The environmental effect of O causes the extensive concern of people, many international climate change research projects all they to be listed in important grinding
Study carefully content.Nitrous oxide (N2O) being a kind of nitrogen-containing compound that in lower atmosphere layer, content is the highest, it has characteristic infrared absorption,
As air is only second to CO2And CH4One of several main greenhouse gas, be put into Kyoto Protocol and reduce discharging inventory.
Research shows, since the industrial revolution, due to the impact of mankind's activity, and N in air2The concentration of O sharply increases, and arrives
Nineteen ninety has reached 310ppb, but also increases with the speed of annual 0.2-0.3%.N2O is to affect advection outside fluorine removal Lyons
Layer O3The important chemical composition of another kind.N2O retention time in an atmosphere is long, can be transported to stratosphere.In troposphere, N2O is very
Stable, the time of staying is up to 120 years.When being transferred in stratosphere, N2O participates in a series of photochemical reactions, can change into NO
Or NO2, and affect O3Photochemical equilibrium, ultimately result in O3Loss, and then cause the destruction of ozone layer.Research shows, if greatly
N in gas2O concentration doubles, and global seismic temperature not only can be made averagely to rise 0.4 DEG C, and makes the smelly of differing heights in atmosphere
Oxygen concentration reduces 10-16%.
Abroad begin to apply GC-ECD method (gas chromatogram-electron capture detection method) to measure in air at late nineteen seventies
N2O.But the research report that China is in this respect is the most little.
On U.S. scientific magazines in 2009, Ravishankara teaches seminar's research and shows: N2O is in whole 21 century
Consume O3Most important material.But to the N in air2O quantitative analysis the most also rarely has research.Metal-organic framework material
(MOFs) as a kind of novel energy material, not only route of synthesis is varied, structure is marvellous, and has high stability, ratio
Surface area scalable, can organic functional, its have in terms of the energy, gas absorption/separation, medicine and catalysis potential should
With, attract the concern of scientist the most always.2010, DENG SHUGUANG taught the MOFs material that seminar is classical
Material, MOF-5 and MOF-177 are to N2O carries out the absorption research under room temperature, but effect is the most undesirable.Frame based on MOFs material
The excellent properties such as shelf structure adjustability and high stability, we to it at N2O seizure aspect has done quantitative study, and result shows to close
The material become is to N2O has good absorption property.
Summary of the invention
It is an object of the invention to for N2O is powerful greenhouse gases and the consumption destruction to ozone layer thereof, it is provided that a kind of
For N2Metal-organic framework material of O absorption and preparation method thereof, this material has preferable acid-proof alkaline and heat stability.
Technical scheme:
A kind of for N2The metal-organic framework material of O absorption, chemical formula is { [(CH3)2NH2]19[Ni24(bptc)9
(H2O)12(μ2-O)12(μ3-OH)4(μ4-OH)3]·5H2O·DMA}n, in formula: n is 1 to the most infinite natural number, and bptc is 3,
3 ', 5,5 '-biphenyl tetracarboxylic carboxylic acid ion, DMA is N,N-dimethylacetamide, (CH3)2NH2For dimethylamine cation；This gold
Belong to organic framework materials by transition metal Ni2+Ion constitutes three dimensional network with organic ligand by coordinate bond or intermolecular force
Network structure, wherein organic ligand is 3,3 ', 5,5 '-biphenyl tetracarboxylic carboxylic carboxylic；Containing two kinds of coordination modes in this tridimensional network
Different Ni2+Ion, every three Ni1 ions form three core bunch Ni3, every eight Ni2 ions form eight core bunch Ni8,
And every eight Ni3Bunch with part formed an aperture be the cage of 1.2nm, the most every six Ni8Bunch and eight Ni3Bunch formed one
Individual aperture is the cage of 1.9nm, and the two cage connects formation three-dimensional frame structure by part.
A kind of described for N2The preparation method of the metal-organic framework materials of O absorption, step is as follows:
1) by 3,3 ', 5,5 '-biphenyl tetracarboxylic carboxylic acid, four hydration nickel acetates, a hydronium(ion) lithium oxide add N, N-dimethyl
In acetamide (DMA) and distilled water, stir 20min under room temperature, be subsequently adding the concentrated nitric acid that concentration is 16mol/L and mixed
Liquid；
2) above-mentioned mixed liquor is heated 72 hours at 140 DEG C, then makes temperature drop to room temperature with the speed of 2 DEG C/min,
It is filtrated to get green bulk crystals；
3) by above-mentioned crystal distilled water wash 3-5 time, then wash 2 times with methanol, be dried in atmosphere, prepare and be used for
N2The metal-organic framework material of O absorption.
Described 3,3 ', 5,5 '-biphenyl tetracarboxylic carboxylic acid, four hydration nickel acetate, a hydronium(ion) lithium oxide, the mol ratios of concentrated nitric acid
For 0.05mmol:0.15mmol:0.1mmol:3mL；One hydronium(ion) lithium oxide and distilled water and DMAC N,N' dimethyl acetamide (DMA)
Amount ratio be 0.1mmol:1.5mL:3mL.
A kind of described for N2The application of the metal-organic framework material of O absorption: for N2The storage of O, method is to prepare
Metal-organic framework materials soak 72 hours with the water in exchange duct and DMAC N,N' dimethyl acetamide (DMA) point with methanol
Son, and change a methanol solvate every day to realize solvent exchange completely；Metal-organic framework material after exchange is existed
Heat at vacuum 1mbar and 160 DEG C 12 hours to remove the methanol molecules in duct, be filled into and deposit N2The dress of O adsorbent
In putting standby.
The invention have the advantage that 1) this material has preferable ph stability, keeps steady in the aqueous solution that pH is 3-13
Fixed, be conducive to reality application；2) heat stability of material is high, and alternating temperature XRD shows that framework still keeps stable when 375 DEG C；3) exist
During 273K/1bar, material is to N2The adsorbance of O is 116cm3g-1, during 298K/1bar, to N2The adsorbance of O is 72cm3g-1,
N2The absorption aspect of O has good application prospect.
Accompanying drawing explanation
Fig. 1 is the crystal structure figure of this metal-organic framework materials, wherein: Fig. 1 (a): for this metal-organic framework material
Asymmetric cell figure, Fig. 1 (b) is the basket structure of a diameter of 1.2nm in this metal organic frame, and Fig. 1 (c) is that this metal is organic
The basket structure of a diameter of 1.9nm in framework, Fig. 1 (d) is this metal organic frame topological Simplification figure in crystallography c direction.
Fig. 2 is the ph stability test figure of this metal-organic framework materials, for by this metal-organic framework material respectively
Soak the powder diagram after 24 hours in the Acidity of Aikalinity aqueous solution of pH=3,5,8,11,12,13.
Fig. 3 is the alternating temperature powder diagram of this metal-organic framework material.
Fig. 4 is the gas absorption curve chart of this metal-organic framework material.
Fig. 5 is the sample after the exchange of this metal-organic framework material methanol, the sample after placing month in atmosphere,
And the powder diffractogram of the sample after gas absorption.
Detailed description of the invention
Embodiment:
A kind of for N2The metal-organic framework material of O absorption, chemical formula is { [(CH3)2NH2]19[Ni24(bptc)9
(H2O)12(μ2-O)12(μ3-OH)4(μ4-OH)3]·5H2O·DMA}n, in formula: n is 1 to the most infinite natural number, and bptc is 3,
3 ', 5,5 '-biphenyl tetracarboxylic carboxylic acid ion, DMA is N,N-dimethylacetamide, (CH3)2NH2For dimethylamine cation；This gold
Belong to organic framework materials by transition metal Ni2+Ion constitutes three dimensional network with organic ligand by coordinate bond or intermolecular force
Network structure, wherein organic ligand is 3,3 ', 5,5 '-biphenyl tetracarboxylic carboxylic carboxylic；Containing two kinds of coordination modes in this tridimensional network
Different Ni2+Ion, every three Ni1 ions form three core bunch Ni3, every eight Ni2 ions form eight core bunch Ni8,
And every eight Ni3Bunch with part formed an aperture be the cage of 1.2nm, the most every six Ni8Bunch and eight Ni3Bunch formed one
Individual aperture is the cage of 1.9nm, and the two cage connects formation three-dimensional frame structure by part.
A kind of described for N2The preparation method of the metal-organic framework materials of O absorption, step is as follows:
1) by 3,3 ', 5,5 '-biphenyl tetracarboxylic carboxylic acid of 0.05mmol, the four hydration nickel acetates of 0.15mmol, 0.1mmol
One hydronium(ion) lithium oxide adds in 3mLN, N-dimethyl acetylamide (DMA) and 1.5mL distilled water, stirs 20min, so under room temperature
Rear addition 0.15mL concentration is that the concentrated nitric acid of 16mol/L obtains mixed liquor；
2) above-mentioned mixed liquor is heated 72 hours at 140 DEG C, then makes temperature drop to room temperature with the speed of 2 DEG C/min,
It is filtrated to get green bulk crystals；
3) by above-mentioned crystal distilled water wash 3 times, then wash 2 times with methanol, be dried in atmosphere, prepare and be used for
N2Metal-organic framework material 19mg of O absorption, productivity is 51%.
Measure crystal structure by Supernova type X-ray single crystal diffractometer, use through graphite monochromator monochromatization
Mo-KαRayFor Incident Irradiation Source, withScan mode collects point diffraction, repaiies through method of least square
Just their coordinate and anisotropic parameters thereof, the position of hydrogen atom is obtained by theory hydrogenation, and all of calculating uses SHELXL-
97 and SHELXL-97 program bags are carried out.Result shows: the structural formula of this metal-organic framework material is { [(CH3)2NH2]19
[Ni24(bptc)9(H2O)12(μ2-O)12(μ3-OH)4(μ4-OH)3]·5H2O·DMA}n, belong to the highest symmetric cubic crystal
System, space group is Fm-3c, and cell parameter isα=β=γ=90 °, unit cell volume isZ=16, Dc=1.063mg/mm3。
Fig. 1 is the crystal structure figure of this metal-organic framework materials, wherein: Fig. 1 (a): for this metal-organic framework material
Asymmetric cell figure, Fig. 1 (b) is the basket structure of a diameter of 1.2nm in this metal organic frame, and Fig. 1 (c) is that this metal is organic
The basket structure of a diameter of 1.9nm in framework, Fig. 1 (d) is this metal organic frame topological Simplification figure in crystallography c direction.Figure
In show: Ni1 is hexa-coordinate, and four carboxyl oxygens from part, the oxygen from hydrone, and one from μ3-OH
Oxygen atom ligand.Ni2 is also hexa-coordinate, but coordination environment is different from Ni1, and two carbonyl atom O deriving from part,
Three from μ4The oxygen atom of-OH and one are from μ2The oxygen atom ligand of-O.At the Ni that both coordination modes are different2+Ion
In, every three Ni1 ions form three cores bunch, and every eight Ni2 ions form eight cores bunch.And every eight Ni3Bunch with
Part forms the cage structure of a diameter of 1.2nm in a hole；The most every six Ni8Bunch and eight Ni3Bunch formed one bigger
Cage, aperture is 1.9nm.The two cage connects formation three-dimensional frame structure by part.
Performance detects:
The metal organic frame of acquisition is separately immersed in the Acidity of Aikalinity aqueous solution of pH=3,5,8,11,12,13 24 little
Shi Hou, filters crystal, is dried in atmosphere, and carries out powder diffraction (XRD) test respectively.Fig. 2 is this metal-organic framework
The ph stability test figure of material, shows in figure: the diffraction maximum of the crystal after the crystal diffraction peak of simulation and immersion soda acid
Matching, show that the frame structure of material keeps constant, the metal-organic framework materials of the present invention has very in acid-base solution
Good stability.
For the heat stability of validation framework, it is carried out alternating temperature powder diffraction test.Fig. 3 is this metal organic frame material
The alternating temperature powder diagram of material.Figure shows: start to be gradually heated to 400 DEG C from 50 DEG C by this frame material.375 DEG C with
Under, the powder diffraction peak of this material matches with the powder diffraction peak of simulation, illustrates that framework keeps stable.When 400 degrees Celsius,
Basic diffraction maximum has disappeared, and illustrates that framework has caved in.
A kind of described for N2The application of the metal-organic framework material of O absorption: for N2The storage of O, method is to prepare
Metal-organic framework materials soak 72 hours with the water in exchange duct and DMAC N,N' dimethyl acetamide (DMA) point with methanol
Son, and change a methanol solvate every day to realize solvent exchange completely；Metal-organic framework material after exchange is existed
Heat at vacuum 1mbar and 160 DEG C 12 hours to remove the methanol molecules in duct, be filled into and deposit N2The dress of O adsorbent
In putting standby, obtain carrying out the metal-organic framework material of absorption test.
Utilize Quantachrome IQ2Gas absorption instrument records gas absorption data, tests 273K's and 298K respectively
N2O adsorption curve.Fig. 4 is the gas absorption curve chart of this metal-organic framework material, shows in figure: this material is at 273K/
To N during 1bar and 298K/1bar2The adsorbance of O respectively reaches 116cm3g-1And 72cm3g-1.Illustrate that this hybrid material is often
There is under temperature good N2O capturing ability.
Fig. 5 be the sample after the exchange of this metal-organic framework material methanol, in atmosphere place the sample after month,
And the XRD spectra of the sample after gas absorption.Result shows: the sample after methanol exchange is at the XRD after absorption test
Collection of illustrative plates is fitted like a glove with the XRD figure spectrum simulated by single crystal data, and the crystal structure of illustrative material is not destroyed, Ke Yichong
Multiple utilization.XRD spectra after this sample is placed one month in atmosphere is also identical with the XRD of theoretical modeling, illustrates that this material exists
In air highly stable.
Claims (4)
1. one kind is used for N2The metal-organic framework material of O absorption, it is characterised in that: chemical formula is { [(CH3)2NH2]19[Ni24
(bptc)9(H2O)12(μ2-O)12(μ3-OH)4(μ4-OH)3]·5H2O·DMA}n, in formula: n is 1 to the most infinite natural number,
Bptc is 3,3 ', 5, and 5 '-biphenyl tetracarboxylic carboxylic acid ion, DMA is N,N-dimethylacetamide, (CH3)2NH2For dimethylamine sun from
Son；This metal-organic framework material is by transition metal Ni2+Ion and organic ligand are by coordinate bond or intermolecular force structure
Becoming three-dimensional net structure, wherein organic ligand is 3,3 ', 5, and 5 '-biphenyl tetracarboxylic carboxylic carboxylic；Containing two kinds in this tridimensional network
The Ni that coordination mode is different2+Ion, every three Ni1 ions form three core bunch Ni3, every eight Ni2 ions form one eight
Core bunch Ni8, and every eight Ni3Bunch with part formed an aperture be the cage of 1.2nm, the most every six Ni8Bunch and eight Ni3
Bunch formed an aperture be the cage of 1.9nm, the two cage by part connect formed three-dimensional frame structure.
2. one kind is used for N as claimed in claim 12The preparation method of the metal-organic framework materials of O absorption, it is characterised in that step
Rapid as follows:
1) by 3,3 ', 5,5 '-biphenyl tetracarboxylic carboxylic acid, four hydration nickel acetates, a hydronium(ion) lithium oxide add N, N-dimethylacetamide
In amine (DMA) and distilled water, stir 20min under room temperature, be subsequently adding the concentrated nitric acid that concentration is 16mol/L and obtain mixed liquor；
2) above-mentioned mixed liquor is heated 72 hours at 140 DEG C, then make temperature drop to room temperature with the speed of 2 DEG C/min, filter
Obtain green bulk crystals；
3) by above-mentioned crystal distilled water wash 3-5 time, then wash 2 times with methanol, be dried in atmosphere, prepare for N2O inhales
Attached metal-organic framework material.
The most according to claim 2 for N2The preparation method of the metal-organic framework materials of O absorption, it is characterised in that: institute
State 3,3 ', 5,5 '-biphenyl tetracarboxylic carboxylic acid, four hydration nickel acetates, a hydronium(ion) lithium oxide, the amount ratio of concentrated nitric acid are
0.05mmol:0.15mmol:0.1mmol:3mL；One hydronium(ion) lithium oxide and distilled water and DMAC N,N' dimethyl acetamide (DMA)
Amount ratio is 0.1mmol:1.5mL:3mL.
4. one kind is used for N as claimed in claim 12The application of the metal-organic framework material of O absorption, it is characterised in that: it is used for
N2The storage of O, method be by preparation metal-organic framework materials methanol soak 72 hours with exchange duct in water and N,
N-dimethyl acetylamide (DMA) molecule, and change a methanol solvate every day to realize solvent exchange completely；After exchanging
Metal-organic framework material heat at vacuum 1mbar and 160 DEG C 12 hours to remove the methanol molecules in duct, load
To depositing N2In the device of O adsorbent standby.
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| CN105502317B (en) * | 2015-12-22 | 2017-12-08 | 苏州金宏气体股份有限公司 | A kind of device reclaimed with nitrous oxide purification |
| CN105646185A (en) * | 2016-01-12 | 2016-06-08 | 中国石油大学(华东) | Calcium metal-organic coordination polymer and preparation method thereof |
| CN105753845B (en) * | 2016-03-14 | 2018-07-31 | 北京工业大学 | A kind of metal-organic framework materials and preparation method thereof based on low symmetrical four teeth Pyrazole Ligands Ni |
| CN107497402B (en) * | 2017-09-25 | 2019-12-31 | 江苏大学 | Water-stable dye adsorbent and preparation method thereof |
| CN110256685B (en) * | 2019-05-15 | 2021-11-30 | 中国石油大学(华东) | Nickel-based complex and preparation method and application thereof |
| CN110698687A (en) * | 2019-11-01 | 2020-01-17 | 北京工业大学 | Synthesis method of cadmium-metal-organic framework material |
| CN112076617A (en) * | 2020-09-10 | 2020-12-15 | 奚欢 | Energy-saving recovery processing device for nitrogen oxides in industrial production waste gas |
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